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WIREs Comput Mol Sci
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The CL&Pol polarizable force field for the simulation of ionic liquids and eutectic solvents

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Abstract Molecular dynamics (MD) simulation, and theoretical chemistry in general, have been central tools in the study of ionic liquids (ILs) and eutectic solvents, both of which are fluid phases dominated by ionic interactions and strong hydrogen bonds. These systems are still relatively recent, so the amount of experimental information given their enormous diversity is still scarce. Computational studies have produced several important discoveries, besides helping in the interpretation of experimental findings. Here we review the latest developments in the models describing the interactions and conformations of IL phases with atomic detail, in particular polarizable force fields. In these all‐atom models, the response of electron clouds to their electrostatic environment is represented by induced dipoles, therefore moving beyond the pair‐wise additivity of fixed‐charge force fields. Most of the conceptual framework to develop polarizable force fields has been available and implemented in major MD codes, so the main challenge to develop a useful polarizable model for ILs and eutectic solvents is how to handle their diversity in chemical structures and interactions, in order to build a model that can represent solutions, mixtures and interfaces with materials, and that is not too difficult to extend to new systems. As is often the case, force field development is not only science but it is also an art! The ingredients of successful force fields are often the result of pragmatism and heuristics, rather than mathematical complexity and absolutely rigorous physics (although retaining a sound physical basis in the parameters definitely helps). We focus on the CL&Pol polarizable force field for ILs, protic ionic liquids, and eutectic solvents, improving on previous‐generation fixed charge models. The CL&Pol force field is built as a detailed but extendable and transferable model offering more reliable predictions of thermodynamic, structural, and transport properties, which should contribute to the advancement of the field and towards the design of better solvents, electrolytes, lubricants, and so on. This article is categorized under: Molecular and Statistical Mechanics > Molecular Interactions Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods
Layout of the procedure to obtain the CL&Pol force field from the original CL&P fixed‐charge model
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Constant‐potential simulation of a substituted imidazolium dicyanamide ionic liquid electrolyte near charged MoS2 surfaces, with the polarization of the material represented by the image charge method
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Two hydrogen bonding patterns in ethylammonium nitrate. A linear NH⋯O bond obtained from QM calculations in condensed phase97,101,102 and the CL&Pol force field74 (left) and a bent, shared NH⋯O bond obtained with the empirical potential refinement method from X‐ray and neutron scattering98–100 (right)
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Predicting the density of ILs before and after LJ correction by . NH denotes the dual Nosé–Hoover thermostat, tgNH the temperature‐grouped Nosé–Hoover thermostat; SiCSiC corresponds to dimethyl((trimethylsilyl)methyl)silyl)methyl, to 2,2,4,4‐tetramethylpentyl side chains in imidazolium cations
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Predicted and SAPT‐calculated scaling factors. Empty points are those used in the original CL&Pol development,71 whereas filled points are more recent involving new fragments
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Illustration of the polarization catastrophe in ethylammonium nitrate, a protic IL. The DP on the O atom of the anion leaves its DC and is pulled towards the H atom of the cation head group. Hydrogen atoms are not polarizable and so do not carry a DP
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Short‐range damping of Drude dipole–dipole interactions using a Thole function, (, ) and of charge‐Drude dipole interactions using Tang–Toennies functions, (, )
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Molecular and Statistical Mechanics > Molecular Dynamics and Monte-Carlo Methods
Molecular and Statistical Mechanics > Molecular Interactions

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